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Kinetic Study of Vacancy Oxygen Related Defects in Silicon: - Samples: - Reactions
Kinetic Study of Vacancy Oxygen Related Defects in Silicon: - Samples: - Reactions
defects in silicon
V. Quemener1*, B. Raeissi1, F. Herklotz1, L. Murin1, E.V. Monakhov1 and B.G. Svensson1
1Department
of Physics, Centre for Materials Science and
Nanotechnology, University of Oslo, P.O. Box 1048 Blindern, N-0316 Oslo, Norway
vincent.quemener@smn.uio.no
Introduction
Oxygen is one of the most important impurities in Czochralski-grown silicon, and contributes to the major defects formed during silicon crystallization and high
temperature processing. For instance, oxygen related defects are, presumably, responsible for the light-induced degradation effect, which is known to
dramatically decrease the efficiency of the photovoltaic cells. In particular, electrically active and inactive centers like oxygen complexes (On) and vacancy-
oxygen complexes (VOn) are the most frequently appearing defects. These defects have been the subject of extensive investigations1,2,3,4. However, the
diffusion and dissociation mechanisms associated with the formation and evolution of these defects remain unclear and a thorough investigation needs to be
performed. One of the most successful methods for studying oxygen-containing centers in silicon is the Local Vibrational Mode (LVM) spectroscopy4,5. In
particular, Fourier Transform Infrared (FTIR) absorption has been used to identify vacancy-oxygen complexes VOn (n ≥ 1)6.
Experiment Simulation
• Reactions
• Samples: • Evolution of defects is described by the theory of diffusion-limited
• n-type Cz-Si with oxygen [Oi] and carbon [Cs] of 1x1018 and 5x1014 cm-3. reactions7 and assuming a sequential build-up of the vacancy-oxygen
• Irradiation with 2.5 MeV fast electrons (1x1018 cm-2) at RT. clusters, including diffusion/dissociation reactions.
• Isothermally annealing treatment in nitrogen flow at 350-470oC
temperature range.
• [Oi] and [VOn] defects followed by FTIR at room temperature. The IR
absorption has been carried out using a ISF 125 HR Bruker Fourier
transform IR spectrometer. • Rate equations
• Diffusion: 4𝜋𝑅(𝐷 + 𝐷 ) 𝐴 𝐵 where 𝐷 = 𝑑 𝑒𝑥𝑝 −
• Dissociation: 𝐶 𝐶 where 𝐶 = 𝑐 𝑒𝑥𝑝 −
Results
• Fitting
• FTIR spectra and isothermal annealing
1350 1350
(a) 1300
[Oi] (b) 1300 [Oi]
[VO]
[VO2] [VO]
1250 1250
[VO2]
• Absorption spectrum of the sample [VO3]
[VO4]
6
[VO3]
20 [V] [VO4]
annealed at 425oC. [V]
N, 1015 (cm-3)
N, 1015 (cm-3)
0
isothermal annealing: 0
0 1 2 3 4 100 200 300 400 0,0 0,5 50 100 150 200 250 300 350
time (h)
• After irradiation, only VO is present. 1400
time (h)
1400
(c) [Oi] (d) [Oi]
• After annealing, one can observe 1300
1200
[VO]
1300
1200
[VO]
[VO2]
the successive formation of VO2, Figure 1: Absorption spectra after irradiation and after
[VO2]
[VO3] 8 [VO3]
7
VO3 and VO4. isothermal annealing at 425oC for different time steps.
6
[VO4]
[V]
[VO4]
[V]
N, 10 (cm )
N, 1015 (cm-3)
-3
6
5
• The concentration of Oi has been monitored by measuring the height of 4
15
For VO, VO2, VO3 and VO4, we used calibration coefficient of 8.5x1016, 2
1
2
• Evolution of vacancy
15
x 10 1400
8,0 1000
1300
(e) 1200
[Oi] (f) 900 [Oi]
o
370 C 1100
[VO] 800 [VO]
7,5 [VO2] [VO2]
400oC [VO3] 8 [VO3]
• The sum of the 4 VOn species 7,0
425oC
450oC
6
[VO4]
[V]
[VO4]
[V]
5
gives information on the evolution
N, 1015 (cm-3)
N, 10 (cm )
470oC 6
-3
6,5 4
3 4
6,0
the system during the annealing 2
2
processes. The evolution of the 5,5
1
0 5 10 15 20 25 0 2 4 6 8 10 12 14 16 18 20
annealing tell us if other defects 4,5 time (h) time (h)
• At higher temperature: Slight decrease of [V] with the annealing time, which ln(Diff)
-10
ln(D)
ln(D)
VOln(Diss)
ln(D)
ln(D)
1.71 ± 0.01 0.026 ± 0.001
• At temperature higher than 450oC: [V] increases slightly at the beginning of VOln(D) 2.02 ± 0.04 0.0005
ln(D)
ln(D)
ln(D) 3
ln(D)
-15
ln(D) ln(D)
ln(D)
isothermal annealing. This indicates that other defects contribute in the ln(D)
-45
formation of the VOn defects. diff Oi -20
Dissociation
diff VO Ea (eV) c0 (s-1)
-50 diff VO2
X 2.73 1.8x1014
Irradiation creates other defects like vacancy clusters with oxygen complexes. Thus, we diff VO3
-25 VO2 2.40 ± 0.02 5x1011
add a defect X in the simulation which breaks up at high temperature and provides 16 17 18 19 16 17 18 19
VO4 2.57 ± 0.05 4x1012
1/kT 1/kT
additional vacancies through VO3
Figure 4: Arrhenius plot of the diffusion and dissociation Table 1: Activation energies and prefactors of
parameters extracted from the simulation diffusion and dissociation of the defects.
References
[1] J.W. Corbett et al., Phys. Rev. 135 (1964) A1381. [5] L.I. Murin, et al., Phys. Rev. Lett., 73, No. 1, 93–96 (1998).
[2] J.L. Lindström, et al., Mater. Sci. Forum, 367, 258–263, (1997). [6] L.I. Murin, et al., Solid State Phenomena, 108–109, 267–272 (2005).
[3] J.L. Lindström, et al., Solid State Phenomena, 69–70, 297 (1999). [7] T.R. Waite, Phys. Rev. 107, 463 (1957).
[4] J.L. Lindström, et al., Nuclear Inst. Meth. Phys. Res. B, 186, 121-125 (2002).